Two new 3D bismuth containing coordination polymers are reported along with their single crystal structures and SHG properties. Compound 1: Bi2O2(pydc) (pydc = pyridine-2, 5-dicarboxylate), crystallizes in the monoclinic, polar space group, P2(1) (a=9.6479(9) angstrom, b=4.2349(4)angstrom, c=11.9615(11) angstrom, beta=109.587(1)degrees), which contains Bi2O2 chains that are connected into a 3D structure via the pydc ligands. Compound 2: Bi4Na4(1R3S-cam)(8)(EtOH)(3.1)(H2O)(3.4) (1R3S cam =1R3S-camphoric acid) crystallizes in the monoclinic, polar space group, P2(1) (a=19.0855(7) angstrom, b =13.7706(5) angstrom, c=19.2429(7) angstrom, beta=90.701(1)degrees) and is a true 3D coordination polymer. These are two example of SHG compounds prepared using unsymmetric ligands (compound 1) or chiral ligands (compound 2), together with metals that often exhibit stereochemically-active lone pairs, such as Bi3+, a synthetic approach that resulted in polar, non-centrosymmetric, 3D metal-organic coordination polymer. (C) 2012 Elsevier Inc. All rights reserved.